US7910216B2 - Process for the production of organosilsesquioxanes - Google Patents

Process for the production of organosilsesquioxanes Download PDF

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US7910216B2
US7910216B2 US11/424,513 US42451306A US7910216B2 US 7910216 B2 US7910216 B2 US 7910216B2 US 42451306 A US42451306 A US 42451306A US 7910216 B2 US7910216 B2 US 7910216B2
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hydrolysable
monomer precursors
inorganic
composition
process according
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US20070122636A1 (en
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Alan Taylor
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Welding Institute England
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Welding Institute England
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Priority to DE602006014021T priority Critical patent/DE602006014021D1/de
Priority to JP2008541804A priority patent/JP5089602B2/ja
Priority to CN2006800514850A priority patent/CN101365736B/zh
Priority to BRPI0619047-2A priority patent/BRPI0619047A2/pt
Priority to AT06794701T priority patent/ATE466041T1/de
Priority to RU2008126275A priority patent/RU2414484C2/ru
Priority to CA2632254A priority patent/CA2632254C/en
Priority to KR1020087015575A priority patent/KR20080072751A/ko
Priority to EP06794701A priority patent/EP1957563B1/en
Priority to PCT/GB2006/003750 priority patent/WO2007060387A1/en
Priority to PL06794701T priority patent/PL1957563T3/pl
Priority to AU2006318931A priority patent/AU2006318931B2/en
Priority to TW95140014A priority patent/TWI401295B/zh
Publication of US20070122636A1 publication Critical patent/US20070122636A1/en
Publication of US7910216B2 publication Critical patent/US7910216B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a process for the production of organosilsesquioxanes, and to the use of a composition comprising organosilsesquioxanes to provide a protective coating on a substrate so as to impart to the substrate resistance to mechanical and chemical damage, while at the same time maintaining excellent optical properties, and as a bulk material.
  • Organosilsesquioxanes are silicon-oxygen based frameworks having the general formula (RSiO 1.5 ) n , in which n is an even number ⁇ 4.
  • Organosilsesquioxanes which have a very specific structure, for example a compound having the formula (RSiO 1.5 ) 8 has an octahedral cage structure, are referred to in the field as organooligosilsequioxanes or polyhedral oligomeric silsesquiloxanes (or POSS®).
  • Organosilsesquioxanes have the potential to offer good mechanical properties, for example as coatings with good abrasion resistance, and can be formulated to have good chemical resistance, for instance as embodied by hydrolytic stability or stability to UV degradation. These and other properties render the organosilsesquioxanes useful as protective coatings for a wide variety of substrates, particularly polymer-based materials, such as acrylic polymers and polycarbonates, which are routinely used as alternatives to glass in many situations where the weight, tendency to shatter or expense of glass contraindicates its use.
  • a process for preparing a composition comprising organosilsesquioxanes comprising the following steps:
  • each Y group is the same as or different to each other Y group and is selected from chemically-reactive groups such that each Si—Y bond is hydrolysable to form a Si—OH bond, to form inorganic monomers, and allowing partial condensation of the inorganic monomers to form a liquid composition comprising inorganic oligomers;
  • compositions may comprise organosilsesquioxanes having one or more organic functionalities and/or having completely or incompletely condensed structures. Furthermore, the compositions may or may not comprise only organo-oligosesquioxanes.
  • composition comprising organosilsesquioxanes are obtainable by the above-described process.
  • compositions include the application of the above-described compositions to a variety of substrates, the coated substrates themselves, articles made from the above-described compositions, and use of the above-described compositions as bonding agents.
  • compositions of the present invention are capable of providing coatings that confer abrasion resistance, hydrolytic stability and stability to UV degradation to a wide variety of substrates, particularly plastics substrates, and can be fine tuned to have other properties depending upon the nature of the functionalities incorporated therein and the conditions utilised in their preparation.
  • the process of the present invention involves a two-step hydrolysis/condensation reaction and subsequent drying, and optionally curing, of the resulting composition.
  • hydrolysable inorganic monomer precursors of which at least 50 mole % have the formula RSiY 3 (referred to as “first” hydrolysable monomer precursors”), are partially hydrolysed and allowed to undergo some condensation, but not complete condensation, to form inorganic oligomers that will form the building blocks for the final organosilsesquioxanes molecules.
  • the inorganic oligomers are quenched by addition to, or addition thereto, of a relatively large amount of water, which has the effect of causing rapid condensation of the inorganic oligomers.
  • degree of condensation may vary somewhat, up to essentially complete condensation of those oligomers.
  • composition produced is a matter for conjecture, but is not important given the beneficial mechanical and chemical properties achieved.
  • an “hydrolysable inorganic monomer precursor” we mean any inorganic molecule which is activated by hydrolysis to a polymerisable inorganic monomer, which, on polycondensation with similar hydrolysed or partially hydrolysed monomers, forms inorganic oligomers, and ultimately an inorganic network.
  • the term “inorganic” is used to denote the presence in the precursor molecule of an inorganic element, typically one giving rise to an oxide ceramic material, e.g. silicon, aluminium, titanium, zirconium, yttrium, or other transition metals.
  • the first hydrolysable inorganic monomer precursors, RSiY 3 may be selected from a variety of materials. However, it is critical that the R—Si bond should not be hydrolysable, as otherwise the organic group R may be lost to the final structure. It is preferred that group R itself is chemically stable, and in particular that it is stable to hydrolysis in the presence of water or moisture.
  • Suitable examples of the group R include hydrogen, and optionally substituted (cyclo)alkyl, aryl, alkenyl, amido, epoxy, (meth)acrylic, styrenic, nitrile, anhydride, ester, phosphino, halide, amino, mercapto and cyanate groups, and mixtures thereof.
  • Preferred R groups are selected from (cyclo)alkyl, aryl and alkenyl groups, optionally substituted with groups selected tram epoxy, vinyl, (meth)acrylic and cyanate groups.
  • the size of the R group be selected so that the final composition is liquid in nature, enabling its application as a coating composition.
  • the Y groups in the first hydrolysable inorganic monomer precursors may be the same as or different to one another, although typically they are the same.
  • the Si—Y bond is a highly reactive bond which readily undergoes hydrolysis to form a silanol group, ie. Si—OH.
  • Suitable examples of Y groups are alkoxy, acetoxy groups, amine and nitrate groups and halogen atoms.
  • condensation may proceed in a heterofunctional manner when different hydrolysable inorganic monomer precursors are present, as is discussed in more detail below, such as shown in the following two reaction sequences: —Si—OH+ClSi— ⁇ —Si—O—Si—+HCl —Si—OH+ROSi— ⁇ —Si—O—Si—+ROH
  • the process of the present invention may involve the use of a single type of hydrolysable inorganic monomer precursor, having the formula RSiY 3 .
  • different hydrolysable inorganic monomer precursors may be used, for instance differing in the nature and/or number of organic groups R and/or the nature and/or number of the hydrolysable groups Y.
  • first hydrolysable inorganic monomer precursors may be used having different R groups, for instance RSiY 3 , R 1 SiY 3 , etc., the R and R 1 groups being selected to provide particular mechanical and/or chemical properties in the final product.
  • the present invention is not limited to the use of two different types of first hydrolysable monomer precursors, but may involve the use of more than two different types of the monomer precursors, provided that adequate control over the process is maintained so as to achieve the desired level of incorporation of the different R groups into the final product.
  • the process may involve the use of hydrolysable inorganic monomer precursors differing in the number of hydrolysable groups Y.
  • hydrolysable inorganic monomer precursors having the general formula R n SiY 4-n , in which n is 0, 2 or 3, R is an organic group, for instance selected from those groups given for R above, the R—Si bond is a non-hydrolysable bond, and the R groups are the same as or different to one another, and each Y group is the same as or different to each other Y group and is selected from chemically-reactive groups such that each Si—Y bond is hydrolysable to form a Si—OH bond, and mixtures of such monomer precursors, may be used in addition to the first hydrolysable monomer precursors, RSiY 3 .
  • these additional monomer precursors are termed “second hydrolysable inorganic monomer precursors”.
  • the nature of the groups R and Y are as defined above for the first organic monomer precursors.
  • the groups R and/or Y in the second hydrolysable inorganic monomer precursors may be the same as or different to the groups R and/or Y in the first hydrolysable inorganic monomer precursors.
  • first hydrolysable inorganic monomer precursors and second hydrolysable inorganic monomer precursors having the formula RSiY 2 or R 3 SiY include:
  • alkyl group may be replaced by cycloalkyl group, an aryl group or an alkenyl group, and may optionally be substituted preferably with a (meth)acrylate group or an epoxy group.
  • hydrolytic stability is desired in the final product, those hydrolysable monomer precursors having hydrolysable R groups should be avoided.
  • Suitable examples of second hydrolysable inorganic monomer precursors having the formula SiY include silicon tetra-alkoxides, such as tetramethoxysilane, tetramethoxysilane, tetraisopropoxy-silane and tetrabutoxysilane.
  • the process may also, or alternatively, involve the use of hydrolysable inorganic monomer precursors containing an inorganic atom other than silicon, for instance having the formula MY n , in which M is typically a metal, n is the valency of the metal, and each Y group is the same or different to one another and is selected from chemically-reactive groups such that each M-Y bond is hydrolysable to a M-OH bond.
  • Suitable examples of such materials include:
  • the process may also, or alternatively, involve the use of hydrolysable inorganic monomer precursors of the generic formula (R 2 Si) x Y 2 , in which x ⁇ 1, the R—Si bond is a non-hydrolysable bond and R is defined above (and each R group may be the as as or different to each other R group) and Y is a chemically reactive group with each Si—Y bond being hydrolysable to Si—OH.
  • Suitable examples of the group Y include chlorine, acetoxy, amine, oxime (ie., R 2 C ⁇ NOSi) and alkoxy,
  • the integer x may vary from 1 to a large number, for instance up to or even greater than 100, giving rise no multi-silicon polymers.
  • hydrolysable inorganic monomer precursors which differ in the number of hydrolysable groups present
  • the hydrophilic/hydrophobic character of the R groups(s) will determine the behaviour of the final product when exposed to water. This behaviour can be modified by appropriate selection of solvent. For example, the tendency towards the repulsion of water of an aliphatic hydrocarbon can be changed by the use of a protic solvent, such as alcohol, compared to an aprotic one, such as tetrahydrofuran.
  • a protic solvent such as alcohol
  • hydrolysis of the different hydrolysable inorganic monomer precursors be conducted separately so as to avoid competition for the water molecules present, which may otherwise result in an inhomogeneous or undesirable distribution or monomers, and in particular the organic groups associated therewith, in the final product.
  • the different inorganic oligomers formed are mixed together prior to subjecting to the quenching step that is to follow.
  • water is either added to the hydrolysable inorganic monomer precursors, or is synthesised in situ.
  • hydrolysis is achieved by formation of an homogeneous mixture with water and, optionally, an organic solvent.
  • the precursors may be dissolved in an organic solvent and water added to the resulting solution in a controlled manner, to avoid the uncontrolled development of agglomerations of partially-hydrolysed molecules.
  • Suitable organic solvents include low boiling point organic liquids, for instance having a boiling point lower than 100° C., such as alcohols.
  • the mixture of water and hydrolysable monomer precursors is mixed to ensure that as many precursor molecules are exposed to water as possible, thereby achieving as homogeneous hydrolysis and condensation as possible.
  • water is to be synthesized in situ in the reaction mixture, this can be achieved, for example, by adding an alcohol to the hydrolysable inorganic monomer precursors and then a weak acid, for example acetic acid, again in a controlled manner.
  • a weak acid for example acetic acid
  • a catalyst may be used to initiate hydrolysis of the hydrolysable inorganic monomer precursors, provided that the catalyst does not react with the inorganic monomer precursors, or affect the nature of the species formed on hydrolysis.
  • Suitable catalysts include mineral acids such as hydrochloric acid, sulphuric acid and nitric acid. Only a small amount of acid is needed for this purpose. Although, depending upon the nature of the inorganic monomer precursors, hydrolysis may proceed spontaneously.
  • the amount of water used for hydrolysis should generally be sufficient to hydrolyse at least one of the hydrolysable bonds present in each of the inorganic monomer precursor molecules. However, preferably the amount of water, and the conditions of the hydrolysis reaction, are selected so as to achieve hydrolysis of only one or at most two of the hydrolysable bonds present in the first hydrolysable inorganic monomer precursors, as this will dictate the types or structure that are achieved in the second step of the process.
  • part of the first step of the process involves at least partial condensation, but not complete condensation, of the monomers formed on hydrolysis to form inorganic oligomers.
  • the degree of condensation which takes place may be determined by, for example, NMR.
  • the degree of condensation is such that the majority of oligomers formed from first hydrolysable monomer precursors have one of the following formulae in which each or some of the R groups may be the same or different:
  • oligomers More preferably a majority of the oligomers have the formula (I), and most preferably most (for instance at least 80 mole % or even at least 90 mole %) of the oligomers have the formula (I).
  • the first, hydrolysis, step of the process can vary in duration, for instance it may take less than an hour or many days, depending upon the properties required in the final product. Longer durations are believed no result in greater connectivity of the resulting inorganic network, and thus greater molecular weight.
  • the mixture is quenched into water to fully hydrolyse the species present and to create conditions that favour complete hydrolysis and further condensation.
  • the detailed nature of the structures created depends upon the nature and concentration of the hydrolysable inorganic monomer precursors used, the solvent, the initial hydrolysing conditions and the co-condensation conditions (time, temperature, pH).
  • the hydrolysis and condensation reactions of the first step of the process may be allowed to proceed for a period ranging from a matter of minutes, typically at least 10 minutes, to 24 hours or more.
  • Quenching can be achieved either by adding water to the liquid composition obtained in the first step of the process, or by adding the liquid composition to water, preferably in a single step.
  • the volume of water used in the quenching step, in combination with any water used in the first step of the process and any water liberated as a result or condensation in than step, should be greater than the stoichiometric amount of water required to achieve total hydrolysis (ie. of all hydrolysable bonds) of all the hydrolysable inorganic monomer precursors.
  • the amount of water is at least twice, and more preferably at least five times, this stoichiometric amount. Further condensation is then allowed to proceed, with stirring, typically for a matter of hours up to a number of days, depending upon the properties required in the final product, and whether it is desired that this product should be only partially condensed or essentially completely condensed.
  • drying includes the removal of any free water and volatiles, for instance by heating to elevated temperature, typically in the range 40 co 80° C.
  • the dried product is then ready for use, for instance as a coating composition, or in bulk form, or it may be further modified prior to use.
  • the product may be cross-linked (or cured) and/or modified to include further organic character to thereby modify the properties of the final product, and/or it may be dehydrated, to reduce or prevent further reaction during use.
  • Solvent may be added to the composition, to improve shelf-life.
  • Cross-linking, or curing, of the product may be achieved through the dependent organic R groups, and/or via residual silanols, to form a variety of 3-dimensional structures.
  • Cross-linking of the organic groups may be achieved by any of the conventional means, for instance by the use of suitable cross-linking reagents or processing conditions, or both, selected to promote intermolecular cross-linking rather than intramolecular cross-linking.
  • suitable cross-linking reagents or processing conditions, or both selected to promote intermolecular cross-linking rather than intramolecular cross-linking.
  • epoxy-containing R groups may be cross-linked, or further polymerised, using reagents which act as accelerators or hardeners, for instance amines, or using Lewis acids.
  • the residual silanols can be made to undergo self-condensation by the use of suitable condensation catalysts, such as triethylamine or tin catalysts, such as tin (II) ethyl hexanoate, or by the selection of suitable reaction conditions known in the art.
  • suitable condensation catalysts such as triethylamine or tin catalysts, such as tin (II) ethyl hexanoate, or by the selection of suitable reaction conditions known in the art.
  • condensation of residual silanols may be achieved by the addition of further silanol-containing species or other species condensable with the residual silanols already present in the product.
  • Suitable materials are those having the generic formula R n SiY′ 4-n , in which n is 0 to 3, R is an organic group as defined above, with each R—Si bond being a non-hydrolysable bond and each R group being the same as or different to each other R group, and Y′ is a species that will allow siloxane formation through silanol condensation or other routes, with each Y′ group being the same as or different to each other Y′ group.
  • silanol-containing species for use in said condensation may be prepared by hydrolysis of hydrolysable inorganic monomer precursors having the generic formula R n SiY′ 4-n , in which each Si—Y′ bond is hydrolysable to Si—OH, with Y′ being selected, for instance, from those groups given for Y above in the context of first hydrolysable inorganic monomer precursors.
  • Such hydrolysis results in species such as, but not limited to, R 2 Si(OH) 2 and R 3 Si(OH).
  • these silanol-containing species will be added to the dried product in the presence of a condensation agent, such as tin (II) ethyl hexanoate, to promote condensation.
  • a condensation agent such as tin (II) ethyl hexanoate
  • Another option mentioned above to effect condensation of the residual silanols is to add other species condensable with those silanols and having the generic formula R n SiY′ 4-n , in which the Si—Y′ bond might not be hydrolysable directly, or at all, to Si—OH.
  • species include materials commonly used as derivatising agents to render glass surfaces hydrophobic, and examples of such materials are well known in the art.
  • materials having the generic formula R 3 SiY′ are suitable for this purpose, in which R is as defined above and Y′ is, for instance, chlorine.
  • one particular example or such a derivatising agent is trimethylchlorosilane.
  • Yet another option to effect silanol condensation is to use a material having the generic formula (R 2 Si) x Y 2 , as defined above in the context of the second hydrolysable inorganic monomer precursors, and to hydrolyse this prior to addition to the dried product.
  • this may be achieved via at least partial dehydration, and preferably substantially complete dehydration.
  • Dehydration is achieved by any of the conventional methods known in the art.
  • the dried product may be dissolved in any suitable solvent, for instance tetrahydrofuran (THF), and free water removed via a molecular sieve.
  • THF tetrahydrofuran
  • dehydration can be further aided by the use of a condensation catalyst, such as triethylamine dissolved in THF and placed over a molecular sieve. After a period of dehydrating the dried product, the volatile solvent is evaporated off to leave a fully or partially dehydrated product.
  • dehydration has been described above as conducted on the dried product, at least partial dehydration may be conducted at earlier stages in the process.
  • the process of the present invention is capable of giving rise to a wide variety of product structures.
  • the tendency towards a “cage” or “ladder” structure in the final product is controlled by the process parameters, for instance the type and/or concentration of the oligomers formed; the solvent employed; the time and temperature of the mixing step; the concentration during the quenching step; the time and temperature under which quenching is carried out; and the method of recovering the final product.
  • the product can still be considered to be reactive, which may or may not be acceptable according co the application to which the material is to be put. If this is unacceptable, various options to achieve further cross-linking, and to reduce reactivity, are described above.
  • cross-linking through organic (ie. R) groups may be initiated prior to coating, and taken to completion either prior to coating or after coating, on to a substrate, for instance using known irradiation (eg. UV), thermal or chemical methods. If cross-linking is taken to completion prior to coating it may be desirable to dissolve the composition in a solvent in order to coat the composition on to a substrate, and then to evaporate the solvent in order to dry the coated composition.
  • organic (ie. R) groups may be initiated prior to coating, and taken to completion either prior to coating or after coating, on to a substrate, for instance using known irradiation (eg. UV), thermal or chemical methods.
  • the product obtained on drying may be mixed with an organic monomer or oligomer (generally referred to in the following as “polymerisable organic species”), which may then be further polymerised, or an organic polymer, such as a latex.
  • an organic monomer or oligomer generally referred to in the following as “polymerisable organic species”
  • the nature of the polymerisable organic species is selected according to the properties required in the final product. Typically, the polymerisable organic species will be selected co provide strength and abrasion-resistance and, where desired, transparency. Furthermore, if chemical resistance is required, for instance resistance to swelling or other damage on contact with a solvent, it is desirable to employ polymerisable organic species capable of forming two-dimensional or three-dimensional, i.e. cross-linked, polymer networks. Such polymerisable organic species may be considered as having difunctional or trifunctional reactivity, in that they possess two or more reactive sites available for polymerization.
  • preferred polymerisable organic species are those which, upon polymerization, form thermosetting polymers.
  • suitable polymerisable organic species include carbonates, esters such as terephthalates, epoxy-containing materials, methyl(meth)acrylates, urethanes, and other difunctional or trifunctional monomers such as some urethane acrylates, unsaturated aliphatic hydrocarbons, and mixtures thereof.
  • Urethane precursors, such as isocyanates or diisocyanates and polyols, and urethane acrylates are particularly preferred, Organometallic monomers may also be used, but in this case they will not contain hydrolysable bonds.
  • the polymerisable organic species polymerise at relatively low temperature, e.g. lower than 150° C., after addition of a suitable initiator, or by irradiation, e.g. with UV or IR light, or bombardment with X-rays or electron beams, so as to be applicable as coatings for thermoplastic materials or thermosetting materials having low melting points.
  • Polymerisation of the polymerisable organic species may be initiated in any conventional manner, which will be determined by the nature of the polymerisable organic species. It will normally involve the use of a polymerization initiator.
  • thermoplastic or thermosetting substrates relatively low temperatures should be used, typically lower than 150° C., and more typically in the range 30 to 80° C. Where a chemical polymerization initiator is used, this may mean delaying addition of this until just prior to, or possibly during, the coating operation.
  • the proportion of organic polymer incorporated into the final product depends on the properties required in the final products.
  • the properties of the final product may be further adjusted through the use of additives conventional in the art.
  • the composition When used as a coating composition, the composition may be applied to a substrate by any conventional means, for example dipping, spraying, roll coating or brushing.
  • the composition may be applied to a wide variety of substrates, and is particularly suitable coating polymeric materials having relatively low melting points, for example of 150° C. or lower.
  • suitable coating polymeric materials include thermoplastic materials and thermosetting materials such as polycarbonates, polyesters such as polyacrylates and polyterephthalates, polyurethanes, and polyacrylics.
  • the enhanced scratch/abrasion and chemical resistance imparted no these materials by way of the coatings of the present invention allows them to be considerably more widely utilised than they are at present.
  • the coating composition may also be used to coat substrates selected from glass, metals including soft metals such as aluminium, brass and silver, ceramic materials, and natural materials such as leather and wood, or synthetic substitutes for these materials. It finds particular use as a coating for glass, and glass substitutes. For example, it may be used to coat building or vehicle, windows and windscreens, e.g. for automobile, aircraft and trains; spectacle lenses; camera lenses; protective visors; optical filters and light casings, e.g. headlamp clusters; compact discs; display screens, e.g. in personal computers and mobile phones; and to protect white goods, e.g. refrigerators and washing machines, and brown goods e.g. audiovisual equipment.
  • composition of the present invention also finds use as a catalyst coating on a variety of substrates.
  • the composition should not be cross-linked, so as to maintain its liquid nature.
  • composition of the present invention also finds use in bonding together at least two articles.
  • the composition may be applied to the surface of one or each article, the surfaces to be bonded brought together, and the composition cured to form a secure bond.
  • the process of the present invention is also capable of producing materials which rind use as bulk materials rather than as coatings.
  • the material may be shaped, for instance by moulding, or otherwise formed into a wide variety of different articles.
  • the present invention is further illustrated by the following Examples.
  • Example 1 10.0 g of the resin produced in Example 1 was diluted with 30.0 g of IMS and 0.1 g of the photoinitiator Irgacure 184 was added. After thorough mixing this solution was flow coated onto a Lexan polycarbonate plaque. The coated plaque was dried in an air atmosphere for 5 minutes at 50° C. and then cured using UV light.
  • Example 1 9.0 g of the resin produced in Example 1 was diluted with 27.0 g of industrial methylated spirit and stirred to give an homogeneous solution. To this solution 1.0 g of aliphatic urethane acrylate 260GP25 was added and 0.1 g of the photoinitiator Irgacure 184. After stirring to achieve an homogeneous solution, the liquid was deposited by flow coating onto a Lexan polycarbonate plaque. The coated plaque was dried in an air atmosphere for 5 minutes at 50° C. and then cured using UV light.
  • Example 4 10.0 g of the resin produced in Example 4 was diluted with 30.0 g of IMS and 0.1 g of the photoinitiator Irgacure 184 was added, as was 0.1 g of FC4430 (from 3M Corporation) as a flow agent. After thorough mixing this solution was flow coated onto a Lexan polycarbonate plaque. The coated plaque was dried in an air atmosphere for 5 minutes at 50° C. and then cured using UV light.
  • Example 7 5.0 g of the resin produced in Example 7 was diluted in 15.0 g of IMS and stirred to give an homogeneous liquid. To this liquid was added 1.08 g of diaminooctane. The mixture was vigorously stirred for 5 minutes and then deposited as a coating onto a Lexan polycarbonate plaque. The coated plague was then dried and cured in an air atmosphere at 130° C. for 18 hours.
  • Example 7 5.0 g of the resin produced in Example 7 was diluted in 15.0 g of IMS and stirred to give an homogeneous liquid. To this liquid was added 1.02 g of xylylenediamine. The mixture was vigorously stirred for 5 minutes and then deposited as a coating onto a Lexan polycarbonate plaque. The coated plaque was then dried and cured in an air atmosphere at 130° C. for 18 hours.
  • Component A and Component B were separately made up.
  • Component A 7.0 g of 3-glycidoxypropyltrimethoxysilane was placed in a beaker, and an intimate mixture of 5.5 g of IMS and 0.80 g of water was added thereto.
  • Component B 40.0 g of phenyltrimethoxysilane was placed in a beaker, and an intimate mixture of 37.1 g of IMS and 5.45 g of water was added thereto.
  • Components A and B were the stirred, separately, in sealed beakers for about one hour, after which they were combined and stirred for about 4 hours, again in a sealed beaker. This mixture was stirred vigorously for 4 hours, and was then poured (or quenched) into 192 g of distilled water. The quenched mixture was stirred vigorously for at least 18 hours before being poured into a large polypropylene container and heated at approximately 50° C. for approximately 6 hours to remove the water. The remaining viscous liquid (resin) was then recovered.
  • Example 10 5.0 g of the resin produced in Example 10 was diluted in 15.0 g of IMS and stirred to give an homogeneous liquid. To this liquid was added 0.17 g of diaminooctane. The mixture was vigorously stirred for 5 minutes and then deposited as a coating onto a Lexan polycarbonate plaque. The coated plaque was then dried and cured in an air atmosphere at 130° C. for 18 hours.
  • Example 12 5.0 g of the resin produced in Example 12 was diluted in 15.0 g of IMS and stirred to give an homogeneous liquid. To this liquid was added 0.20 g of diaminooctane. The mixture was vigorously stirred for 5 minutes and then deposited as a coating onto a Lexan polycarbonate plaque. The coated plaque was then dried and cured in an air atmosphere at 130° C. for 18 hours.
  • Component A and Component B were separately made up.
  • Component A 40.0 g of 3-glycidoxypropyltrimethoxy-silane was placed in a beaker, and an intimate mixture of 31.1 g of IMS and 4.57 g of water was added thereto.
  • Component B 5.0 g of tetraethoxysilane was placed in a beaker, and an intimate mixture of 4.4 g of IMS and 0.65 g of water was added thereto.
  • Components A and B were the stirred, separately, in sealed beakers for about one hour, after which they were combined and stirred for about 4 hours, again in a sealed beaker. This mixture was stirred vigorously for 4 hours, and was then poured (or quenched) into 172 g of distilled water. The quenched mixture was stirred vigorously for at least 18 hours before being poured into a large polypropylene container and heated at approximately 50° C. for approximately 6 hours to remove the water. The remaining viscous liquid (resin) was then recovered.
  • Example 4 1.5 g of the resin produced in Example 4 was dissolved in a mixture of 0.25 g triethylamine and 4.59 of THF. The solution was then placed over dried 4A type molecular sieve. After 24 hours, the solvent was evaporated off and the dehydrated resin was dissolved in 4.5 g IMS and 0.1 g of photoinitiator Irgacure 184 was added. After thorough mixing, the solution was then deposited by flow coating onto a Lexan polycarbonate plague. The coated plaque was air dried for five minutes and then cured using UV light.
  • Example 4 1.5 g of the resin produced in Example 4 was dissolved in a mixture of 0.25 g triethylamine, 4.5 g of THF and 0.25 g of chlorotrimethylsilane. After 24 hours, the mixture was filtered through a 1 ⁇ m filter to remove the solid chloride salt. The solvent was evaporated off and the resin was dissolved in 4.5 g IMS and 0.1 g of photoinitiator Irgacure 184 was added. After thorough mixing the solution was then deposited by flow coating onto a Lexan polycarbonate plaque. The coated plaque was air dried for five minutes and then cured using UV light.
  • Example 4 1.5 g of the resin produced in Example 4 was dissolved in a mixture of 0.25 g triethylamine, 4.5 g of THF and 0.5 g of diethoxydimethylsilane. The solution was then placed over dried 4A type molecular sieve. After 24 hours, the solvent was evaporated off and the resin was dissolved in 4.5 g IMS and 0.1 g or photoinitiator Irgacure 184 was added. After thorough mixing the solution was then deposited by flow coating onto a Lexan polycarbonate plaque. The coated plaque was air dried for five minutes and then cured using UV light.

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Application Number Priority Date Filing Date Title
EP06794701A EP1957563B1 (en) 2005-11-28 2006-10-09 Process for the production of organosilsesquioxanes
PCT/GB2006/003750 WO2007060387A1 (en) 2005-11-28 2006-10-09 Process for the production of organosilsesquioxanes
CN2006800514850A CN101365736B (zh) 2005-11-28 2006-10-09 制备有机硅倍半氧烷的方法
BRPI0619047-2A BRPI0619047A2 (pt) 2005-11-28 2006-10-09 processo para a formação de uma composição que compreende organossilsesquioxanos, composição, e, processos para fornecer um revestimento sobre um substrato, e para a união de pelo menos dois artigos
AT06794701T ATE466041T1 (de) 2005-11-28 2006-10-09 Verfahren zur herstellung von organosilsesquioxanen
RU2008126275A RU2414484C2 (ru) 2005-11-28 2006-10-09 Способ получения органосилсесквиоксанов
CA2632254A CA2632254C (en) 2005-11-28 2006-10-09 Process for the production of organosilsesquioxanes
KR1020087015575A KR20080072751A (ko) 2005-11-28 2006-10-09 유기실세스퀴옥산의 제조방법
DE602006014021T DE602006014021D1 (de) 2005-11-28 2006-10-09 Verfahren zur herstellung von organosilsesquioxanen
JP2008541804A JP5089602B2 (ja) 2005-11-28 2006-10-09 オルガノシルセスキオキサンの製造方法
PL06794701T PL1957563T3 (pl) 2005-11-28 2006-10-09 Sposób wytwarzania organosilseskwioksanów
AU2006318931A AU2006318931B2 (en) 2005-11-28 2006-10-09 Process for the production of organosilsesquioxanes
TW95140014A TWI401295B (zh) 2005-11-28 2006-10-30 用以製造有機倍半矽氧烷的方法
JP2012117582A JP2012197443A (ja) 2005-11-28 2012-05-23 オルガノシルセスキオキサンの製造方法

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JP6213126B2 (ja) * 2012-10-25 2017-10-18 セントラル硝子株式会社 接着性組成物およびその接着方法、および接着後の剥離方法
WO2014119282A1 (ja) * 2013-01-29 2014-08-07 日本曹達株式会社 有機シラン系組成物
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RU2643367C1 (ru) * 2017-05-11 2018-02-01 Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") Способ получения метил(фенил) силоксановых олигомеров с концевыми трифенилсилильными группами
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ATE466041T1 (de) 2010-05-15
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US20070122636A1 (en) 2007-05-31
RU2008126275A (ru) 2010-01-10
KR20080072751A (ko) 2008-08-06
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CA2632254C (en) 2015-11-17
AU2006318931A1 (en) 2007-05-31
AU2006318931B2 (en) 2011-01-20
EP1957563B1 (en) 2010-04-28
BRPI0619047A2 (pt) 2012-07-03
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CN101365736B (zh) 2012-06-20
CN101365736A (zh) 2009-02-11
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TW200722481A (en) 2007-06-16

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